Lecture Topic 3: Industrial Organic Chemistry Ref: “Organic Building Blocks of the Chemical...
-
Upload
frank-norton -
Category
Documents
-
view
239 -
download
0
Transcript of Lecture Topic 3: Industrial Organic Chemistry Ref: “Organic Building Blocks of the Chemical...
Lecture Topic 3: Industrial Organic Chemistry
Ref: “Organic Building Blocks of the Chemical Industry”, by H.H. Szmant“Industrial Organic Chemistry”, by K. Weissermel and H.-J. Arpe
Premise: Classification of organic chemicals by: • COST and PRODUCTION VOLUME
• BUILDING BLOCKS derived from
Goal: Ability to
1. identify bulk, fine and specialty chemicals
2. give examples of primary building blocks and of C1, C2, C3, C4 and higher acyclic and cyclic organic building blocks
3. trace the manufacture of a commonchemical from primary sources to finalproducts
Genetically modified Food
Irreversible cross contaminationPossibility of new lectins (autoimmune diseases)
Financial risk - importbans in EU, Japan
Which ge do we live in ?(A brief history of organic chemistry)
1850+ Coal Tar (side product of “coal gasification”)
1920+ Acetylene (from CaC2, Reppe Chemistry)
1950+ Ethylene (from oil)
1973+ CH4, CO/H2 (syngas)
Future: CO/H2 from Coal, exothermic (~400 years)
CO2 fixation via: • Plants, Animals (endothermic) • CO2 fixation (endothermic)
1850- Plants, Animals
Cost vs. Demand in the Chemical Industry
Medicinals and other specialties
Dyes
FineChemicals
Flavours, fragrances
Specialties
Organic intermediates
Common plastics
Commodities
Resins, Elastomers
Primary organicbuilding blocks
105 106 107 108 109 1010 101
1 1012
Pseudo-commodities
Inorganic heavy chemicals
Demand (lb/y)
Uni
t cos
t ($/
lb)
0.01
0.1
1
10
>100
Organic Chemical Industry Characteristics
KEY SUCCESS FACTORS
• cost
• technical service
• links with customer
INDUSTRY CHARACTERISTICS BULK CHEMICALS FINE CHEMICALS SPECIALTY CHEMICALS
Long Moderate Short/moderate
> 100 >1,000 >50,000
>10,000t/y <10,000t/y highly variable
<5 $/kg >5 $/kg >10 $/kg
none very low high
low high high
high moderate moderate/low
process process application
Product life cycle
# of products
Product volumes
Product prices
Product differentiation
Value added
Capital intensity
R&D focus
–
–
Example of a Specialty Chemical
E.g., a heat-stabilizer additive for flexible PVC film
Could be a mixture of: Zn and Ca stearates triisononyl phosphite epoxidized soybean oil
Could be formulated as a liquid concentrate with a minimalamount of di(2-ethylhexyl)phthalate.
The producer keeps the exact identities and proportions of the metal soaps, phosphite esters, epoxidized oils, and plasticizers secret, giving the customer only the proportions of additive to be used per 100g of resins.
What is meant by a “Building Block”?
A building block is any (organic) chemical that can be used to synthesize other (organic) chemicals.
There are very few truly primary, large-volume organic building blocks.
These are all obtained more or less directly from:• petroleum refining• natural gas• coal• ammonia• carbon dioxide• renewable resources
Primary, Secondary, and Tertiary Organic Building Blocks that are in the Top 50 Chemicals in the U.S. Economy
Primary Building Blocks Secondary BBs Tertiary BBsEthylene ethylene dichloride vinyl chloride
ethylene oxide ethylene glycolethyl benzene vinyl acetate
Propylene propylene oxideacrylonitrile isopropyl alcoholcumene acetonen-butyl alcohol
Benzene ethyl benzene styrenecumene phenol
acetonebisphenol A
Methanol acetic acid vinyl acetateformaldehydeMTBE
TolueneXylenes terephthalic acid
ButadieneUrea
A Closer Look at the Principle Sources of Primary Organic Building Blocks
Natural Gas: methane (85%) -161.4°Cethane (9%) -88°Cpropane (3%) -42°Cbutanes (1% -0.5°Cnitrogen (1%)
Liquid petroleum gasses (LPGs)
Crude Petroleum : LPGslight naphtha or straight-run gasoline 50-100°Cheavy naphtha ( C10) 150-200°Ckerosene, jet fuel ( C16) 175-275°Cgas oils, diesel fuel ( C25) 200-400°Clubricating oils 350+°Clight fuel oil, heavy fuel oil, bunker oilresidue: asphalt
Boiling pt.
Coal is used as: fuel (electric power plants, etc.)precursor of coke (crude form of elementary C)source of syngas (synthesis gas)
Coal Coke
Coal TarRoad Tar
Pitch
Light OilTar bases
Tar acidsN N N
CH3
CH3
O
NH
MetallurgyFuel & exports
Electrodes and C fibers
Producer gas: N2 (75%), CO2 (14%), CO (10%), Ar (1%)
Water gas: H2 (51%), CO (42%), CO2 (6%), N2 (1%)
CH3
CH2
Carbazole
Fluorene
PhenanthreneAnthracene
H2C CH2
Acenaphthene
Indene Coumarone
CH3
CH3
CH3
Tar
OH
Phenol
CreosoteCresols
Xylenols
Naphtha BTX(benzene, toluene, xylenes)
NH3 (6%)CH4, H2S, CO, H2 (14%) CO H2
Oxo chemicals
O
Cl Cl
MeOH, AcOH, Ac2O
CS2
CCl4
SiC
Rayon
CaC2
R2NS
S
n
acetylene HC CH
C NHCaNcalciumcyanamide
C1 Chemistry
C1 building block Source Use
CH4 (methane) Natural gas energy, H2, CO, CH(4-x)Clx
CO (carbon monoxide) Coal (as Syngas) CH3OH, HCOOH, esters,amides, Oxo acids, etc.
CH3OH (methanol) CO + 2H2 H2CO, MTBE, CH(4-x)Clx,Cracking of C3H8, C4H10 CH3COOH
H2CO (formaldehyde) CH3OH, Cracking of LPG Polymers (UF, PF, POM)
HCOOH (formic acid) CO + H2O Fine chemicals
CO2 (carbon dioxide) Water-gas-shift rxn. Supercritical fluids (SCFs)
CS2 (carbon disulfide) S8 + Coke or CH4 Cellulosics, M+SCN–, thiourea
Cl2CO (phosgene) CO + Cl2 R-C=N=O for polyurethanes
(H2N)2CO (urea) NH3 + CO2 Fertilizer, Resins (UF)
HCN (hydrogen cyanide) HCONH2 - H2O Methacrylonitrile, ClCNbyproduct (acrylonitrile)
C2 ChemistryC2 building block Source Use
CH2=CH2 (ethylene) thermal cracking of natural Feedstock for ~30% of allgas, refinery gas, crude oil petrochemicals!!
Polymers (Polyethylenes etc.)Alphaolefins (LDPE), PVC Polystyrene, Polyvinyl acetate Polyethylene oxide
CH3CH2OH (ethanol) fermentation, Gasoline additive (USA),hydration of ethylene Ethylene by dehydration
(Brazil, India, Peru, Pakistan),Solvent, Esters (ethyl chloride, ethyl acetate)
CH3CH=O (acetaldehyde) Wacker-Hoechst (ethylene) CH3COOH, Acetic anhydride,Monsanto process (MeOH) Peracetic acid CH3C(=O)OOH,
Aldol condensation products
CH3COOH (acetic acid)& Monsanto process (MeOH) Vinyl acetate (PVA), Cellulose CH3COOCOCH3 (acetic Oxidation of C4-C8 hydro- acetate, Solvent, Acetate salts,anhydride) carbons or acetaldehyde Chloroacetic acids
HCCH (acetylene) Coal via CaC2 or 1,4-Butanediol, vinyl acetatefrom hydrocarbons
C3 Chemistry
C3 building block Source Use
CH3CH2CH3 (propane) LPG Propylene, energy
CH3CHCH2 (propene) Thermal cracking of LPG, Polypropylene, Acrylonitrile,natural and refinery gas Oxo products (butyraldehyde,
butanol, etc.),Propylene oxideIsopropanol, Cumene, Oligomers (nonene, dodecene,heptene)
CH3COCH3 Hock process (coproduct) Methyl methacrylate, Methyl(acetone) Isopropanol (dehydrogen’n) isobutyl ketone, Bisphenol A,
Wacker-Hoechst (propene) Aldol condensation products,Solvent
CH3CH2COOH CH2CH2 (hydroformylation) Food preservative, Amyl and(propionic acid) Vinyl propionate, Herbicides
C4 Chemistry
C4 building block Source Use
C4H10 (butanes) LPG 1-Butene, Maleic anhydride,MTBE, thiophene
C4H8 (butenes, isobutene) Cracking of Cn4 Polymer/alkylate gasoline,Polymers/copolymers, alcohols
C4H9OH (butyl alcohols) Propene, acetaldehyde MEK, Solvent, Fuel additive
CH3(CH2)2CHO Propene, acetaldehyde 2-Ethylhexanol, Trimethylol-(butyraldehydes) propane
Maleic anhydride Oxidation of C4-feedstocks Unsaturated polyester resins,
Benzene (V2O5 catalyst) Fumaric acid, Pesticides
HO(CH2)4OH Acetylene poly(1,4-butylene terphthalate) (1,4-butanediol) 1,3-butadiene THF, H2N(C4H8)NH2
H2C=CHCH=CH2 Cracking of Cn4 Elastomers (i.e., synthetic (1,3-butadiene) rubbers), Chloroprene, THF
O OO
C5 and Higher Acyclic Building Blocks
Primary Building Blocks Source(s) Use
Petroleum: CnHn+2 (n5) Fossil fuels Solvent, Fuel, Lubricant,(pentanes, hexanes, heptanes, etc., Alkylbenzenes, Alcohols,and other n-paraffins) Chlorinated paraffins,
Lower m.w. alkanes/olefins
Mineral waxes: Ozocerite, Fossil fuels CoatingsMontan wax (lignite)
Fatty Acids: Lard, Tallow, Palm Renewable PVC stabilizer, Surfactant, oil, Corn oil, Castor oil, etc. (animal/plant) Glycerine, Methyl laurate,
Fatty amines (antistatic agents)
Tall-Oil Fatty Acids (TOFA) Renewable Fuel in pulping operations,(pulp byproduct) Dimer/trimer acids for coatings
Terpenes Renewable Fragrance/flavour “essential”(plant) oils, Turpentine
Fermentation Products: Renewable H2S removal from refinery gas, amyl alcohols, carboxylic acids, (plant) Food industry, Pharmaceuticals, Monosodium glutamate (MSG) Laundry products, etc.
Cyclic Building Blocks - Aromatics
Building blocks Source Use
Benzene Coal, Oil, Petroleum Ethylbenzene (for styrene), C6H6 (thermal/catalytic process) Cumene (for phenol/acetone),
Cyclohexane, Nitroenzene
Toluene Coal, Oil, Petroleum Solvent, Benzoic acid, Phenol, C6H5CH3 (thermal/catalytic process) Nitrotoluenes, aminotoluenes
Xylenes Coal, Oil, Petroleum Phthalic acids and anhydrides C6H4(CH3)2 (thermal/catalytic process) (plasticizers, synthetic fibers)
Cumene C6H5CH(CH3)2 Benzene Hock process (phenol/acetone)
Phenol C6H5OH Cumene (Hock process) Phenol resins, Bisphenol A,Benzene, Toluene, ε-Caprolactam
Cyclopentadiene C5 cracking fractions, Polymers (for resins, contact Coal tar adhesives, printing ink resin)
Cyclohexane Crude gasoline, Cyclohexanone (feedstock forBenzene (hydrogenation) nylon precursors)
Epichlorohydrin Epoxy resin
• Structural adhesives
• Structural sealants
• Primer paints
• Electrical insulation
• Fiber reinforced plastic composites Bisphenol A or
Brominated Bisphenol A
• Tires• Rubber hoses• Foam for seats• Caulks & sealants• Bumpers & fenders
Vinyl
• Dashboards• Electrical insulation• Vinyl tops• Floor mats
• Body side moldings• Molded armrests
• Exterior & interior trim
• Upholstery • Modular window
frame units
Polyurethanes Polyisocyanates
Cl2Vinyl chloride monomer
Ethylene
Cl2
CO2
Phosgene
Cl2 Allyl chloride
Propylene BTX
Aspirin
O
O OH
CH3
O
Acetyl Salicylic AcidA.S.A.
90% yield
OH
O OH
Salicylic Acid
+ H3C O
O
CH3
O
Acetic anhydride
H3C H
O
Acetaldehyde
Cu(acetate)2
liquid phase50EC, 3-4 bar
O2+
Shawinigan(Canada)
PdCl2 / CuCl2 Wacker-HoechstProcess
H2C CH2 O2+ 0.5
Ethylene
ONaNaOHOH
Phenol
2. H2SO4
Kolbe-Schmittreaction
2. H2SO4
1. O2
Hockprocess
Cumene
+
Benzene Propylene
FOSSIL FUELS:LPG, Coal, Petroleum, etc.
catalyticprocesses
thermalcracking
1. CO2
thermalcracking
liquid phaseT & P > STP
H2SO4
Kellogg/Monsanto
T < 90EC
Origin of the Other Reagents
Cu Mined as an ore and refined
Pd Mined and refined (Sudbury, Ontario: “anode slime”)
H2SO4 H2O + 0.5 O2 + SO2 pyrometallurgical byproduct
O2 Fractional distillation of liquid air
Acetate Acetic acid Methanol + CO (Monsanto process)
NaOH Electrolysis of brine (NaCl + H2O) “chloralkali cell”